Process of dyeing animal fibers and dyes and dyeing compositions therefor



2,750,327 Patented June 12, 1956 PROCESS OF DYEING ANIMAL FIBERS ANDDYES AND DYEING COMPOSITIONS THEREFOR Wolfgang Max Joseph Eckartlt, BadSegeberg, Holstein, Germany, assignor to Lever Brothers Company, NewYork, N. Y., a corporation of Maine No Drawing. Application May 28,1954, Serial No. 433,269

Claims priority, application Great Britain June 1, 1953 9 Claims. (Cl.167-88) This invention relates to novel hair dyes and to hair dyeingcompositions containing the same. It further relates to a process forthe dyeing of animal fibers using the hair dyeing compositions of theinvention.

In my copending application Serial No. 268,125 filed January 24, 1952there is described a dye for use in a composition for dyeing animalfibers, in particular human hair, and having the general formula where Ris an aromatic radical, X is an amino or hydroxyl group, R is analiphatic radical containing at least one hydroxyl group or oneesterified hydroxyl group, m and p are integers each having a value ofat least 1 and n is an integer having a value such that n+p is at least2.

It has now been found that more exact imitations of the natural shadesof hair, especially after the hair has turned grey, can be obtained withcompositions containing dyes similar to those described above, but witha greater proportion of aliphatic radicals which contain at least onehydroxyl group.

The present invention, therefore, provides a dye for use in'acomposition for dyeing animal fibers, in particular human hair, andhaving the general formula where R is an aromatic radical, R R, R arealiphatic radicals containing at least one hydroxyl group and m, n and pare integers having a value of at least 1.

Preferably the group R in the above mentioned formula is a benzeneradical. A preferred class of compounds are those of the formula In theabove formula R R and R may all be the same groups. They may, however,be all different or any two may be the same and a third a dilferentgroup. They may be selected from groups such as CH2CH2OH, -CH2CH2CHzOH,-CH2CHOHCH3,

CH2CH2CH2CH2OH or like groups. Alternatively, either R R or R or allthree or any two of these groups may be a polyoxyalkalene group such aspolyethylene glycol or polypropylene glycol.

Preferably R R and R are all ethylol groups. However, groups with morethan two carbon atoms, for example, those mentioned above and groupswith more than one hydroxyl group may be used with advantage.

When used alone without other dyes for dyeing animal fibers the dyesaccording to the present invention produce deep blue to violet tints.They may be used advantageously in conjunction with other nitro-dyes,for example,

the nitro-dyes described in my aforesaid copending application SerialNo. 268,125 to produce other shades. They possess the valuable propertyof suppressing the reddish tints which other nitro-dyes tend to produce,especially when used on grey hair.

Hence, the present invention also provides a composition for dyeinganimal fibers, in particular human hair, which composition contains theabove-described dyes according to the present invention.

The present invention further provides a process of dyeing animalfibers, in particular human hair, using the above-described composition.

The composition employed for dyeing hair and other animal fibers can beprepared by dissolving or dispersing the dyestuff in water to produce asolution of the desired concentration using, if necessary, aconventional blender or dispersing apparatus. Water-miscible organicsolvents such as ethyl alcohol can be employed to facilitate solution;in this event, the dye can be dissolved first in the alcohol, whichsolution is then diluted with Water to the desired concentration.

The dispersion of the dyestutf may also be facilitated by addition of adetergent or dispersing agent. A detergent such as an alkyl sulfate, e.g., lauryl or myn'styl sulfate, will also facilitate absorption andretention of the dye by the fiber.

It is desirable but not essential to adjust the pH of the dispersion orsolution to 8 or less and preferably in the range from 6.5 to about 7.5.Use of dispersions or solutions having a pH of 8 or less will minimizethe effect of the treatment upon the gloss, texture and strength of thefiber.

The material employed to adjust the pH will be an acid or base such aspotassium carbonate depending upon the initial pH but it should notattack the hair or other fiber.

Buffer combinations may also be employed in order to maintain the pH ofthe dispersion of the solution constant during dyeing.

This composition is then applied to the fiber or hair in such a way asto saturate it throughly therewith. This may conveniently beaccomplished by immersing the material in the liquid or by combing orbrushing out the material and by saturating it with a comb wet with theliquid and by like means known to those skilled in the art.

The intensity and shade of color obtained primarily depend upon thepresence or absence of other dyes, the concentration of the liquid andthe dyeing temperature. Best results are obtained in the temperaturerange from 20 to 30 C. and when the dye concentration does not exceed3%. For most purposes, a concentration in the range from 1 to 2% ispreferable but much less than 1% may be adequate under certaincircumstances.

It will be appreciated by those skilled in the art that the intensity ofshade will also be dependent to some extent upon the dyeing time andupon the nature of the dye. For this reason, specific conditions inevery dyeing cannot be given but those skilled in the art will note fromthe above disclosure and the following examples what conditions toemploy in a given case.

The composition and process of the invention are applicable to animalfibers of all types including human hair and wool.

The preparation and use of the dyes according to the present inventionwill now be illustrated further by the following examples. In theseexamples all parts are given as parts by weight.

Example 1 7.5 parts of l-(p-ethylolamine)-4-amino-3-nitrobenzeneobtained by heating l.4-diamino-3-nitrobenzene with excess ethylenechlorhydrin in the presence of auhygrease":

drous sodium acetate are ground with 6 parts of magnesium carbonate andmixed with 30 parts of ethylene chlorhydrin. Sulfuric acid is then addedto the solution. The undissolved part of the mixture is filtered off andthe remaining solution evaporated to a small volume. The sulfate ofl-(difi-ethylolamino -4-(;3-ethylolamino) -3- nitrobenzene crystallizesout. From this salt the corresponding base may be prepared in the usualway. The pure base melts at 108 C.

When 1 part of a 25% solution of ammonia and 2 parts of wetting agentare added to 1 part of this base mixed with 2 parts of ethanol and themixture diluted with 94 parts of water, a solution is obtained whichwhen used at 30 to 35 C. for dyeing hair imparts a deep ultramarineshade to the hair.

Example 2 1 part of l-(di-fi-ethylolamino)-4-(5-ethylolarnino)-3-nitrobenzene, prepared according to Example 1 and 0.1 part of1:2-di-amino-4-nitrobenzene are mixed with 2 parts of ethanol. 1 part ofa 25% solution of ammonia and 1 part of wetting agent are added and themixture diluted with 97 parts of water. Human grey hair is dyed withthis solution at a temperature of 30 to 35 C. when a natural brown shadewithout any reddish tinge is obtained.

Example 3 13 parts of glycidol (epihydrinalcohol) are mixed with 6 partsof l,4-diamino-3-nitrobenzene. This mixture is lrept for 24 hours at 10C., then for another 24 hours at 20-30 C. The dark-blueviolet coloredreaction product, which containstri-({Ly-dihydroxypmpyl)1,4-diamino-3-nitrobenzene [i. e. 1-(di-B,'-dihydroxypropylamino)-4-(,8,y-dihydr0xypropylamino) 3 nitrobenzene orl-(ls -dihydroxypropylamino) 4 (di-B,--dihydroxypropylamino)-3-nitrobenzene or a mixture of both], isdissolved in 33 parts of 2 N hydrochloric acid and 2 parts of activecarbon are added. After 4 hours the solution is filtered and 62 parts ofwater, 8 parts of aqua ammonia (25%) and 2 parts of the sodium salt oflauryl alcohol sulfate are addedto the filtrate. This dyeing solutionwhen applied to white human hair for 30 minutes at 30 C. dyes the hairwith a blueviolet tint. By adding varying amounts of5-nitro-2,4-diarninotoluene different shades ranging from middle to darkblond may be obtained.

Example 4 13 parts of glycidol (epihydrinalcohol) are mixed with 8 partsof l-(B-ethylolamino)-4-amino-3-nitrobenzene (obtained as described inExample 1). This mixture is kept at -10 C. for 2 days and then foranother 2 days at room temperature. The blueviolet reaction productwhich contains 1,4-diarnino-3-nitrobenzene in which three hydrogen atomsof the amino groups are substi tuted by one hydroxyethyl and twodihydroxypropyl groups is mixed with 160 parts of water and 8 parts ofaqua ammonia (25%). 2 parts of a wetting agent are added together with0.5-0.7 part of 5-nitro-2,4diarninotoluene according to the desiredshade. The so-obtained dyeing solution dyes white hair at 30-40 C. inabout 30 minutes to a light brown color.

Example 5 20 parts of 3-chloro-propanol-1 are mixed with 2 parts of1,4-diamiuo-3-nitrobenzene, 8 parts of anhydrous potassium-carbonate and0.04 part of iodine and heated for 6 hours in an oil bath at atemperature of 130 C. After keeping for 1 day at room temperature themixture is heated again in an oil bath for 9 hours. The precipitated KClis filtered off and after washing with a mixture of ethanol andisopropanol the mixture is concentrated by evaporation. This solutioncontains tri-( y-hydroxypropyl)-1,4-diamino-3-nitrobenzene. To thissolution 70 parts of water, 1 part of ammonium lauryl sulfate and 4parts of aqua ammonia (25%) are added and to the solution is added wateruntil parts by weight are obtained. Then 0.16 part of5-nitro-2,4-diamino toluene are added and the mixture is heated for halfan hour at 60- 70 C. A hair dye solution is obtained which dyes grizzledhair at 35-40 C. to a middle blond shade.

I claim:

1. A process of dyeing animal fibers, in particular human hair, whichcomprises treating hair with an aqueous solution of at least one organicdye of the general formula:

where R is a benzene ring, R R and R are aliphatic radicals of 1-4carbon atoms, inclusive, each containing at least one hydroxyl group andm, n and p are integers having a value of at least 1.

2. A process according to claim 1, in which the dye has the formula inwhich R R and R are aliphatic radicals of 1-4 carbon atoms, inclusive,each containing at least one hydroxyl group.

3. A process according to claim 1 in which R is a benzene ring, R R andR are ethylol groups and m, n and p are 1.

4. A compound for use in dyeing animal fibers, in particular human hair,having the general formula:

where R is a benzene ring, R R and R are aliphatic radicals of 1-4carbon atoms, inclusive, each containing at least one hydroxyl group andm, n and p are integers having a value of at least 1.

5. A compound having the formula:

in which R R and R are aliphatic radicals of 1-4 carbon atoms,inclusive, each containing at least one hydroxyl group.

6. A compound according to claim 4 in which R is a benzene ring, R R andR are ethylol groups and m, n and p are 1.

7. A composition for dyeing animal fibers, in particular human hair,comprising an aqueous solution of the compound of claim 4.

8. A composition for dyeing animal fibers, in particular human hair,comprising an aqueous solution of the compound of claim 5.

9. A composition for dyeing animal fibers, in particular human hair,comprising an aqueous solution of the compound of claim 6.

References Cited in the file of this patent UNITED STATES PATENTS

1. A PROCESS OF DYEING ANIMAL FIBERS, IN PARTICULAR HUMAN HAIR, WHICHCOMPRISES TREATING HAIR WITH AN AQUEOUS SOLUTION OF AT LEAST ONE ORGANICDYE OF THE GENERAL FORMULA: